Polishing Slurries for Polishing Semiconductor Wafers

ABSTRACT

Polishing slurries for polishing semiconductor substrates are disclosed. The polishing slurry may include first and second sets of colloidal silica particles with the second set having a silica content greater than the first set.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/221,839, filed Jul. 28, 2016, which claims the benefit of U.S.Provisional Patent Application No. 62/207,701, filed Aug. 20, 2015, bothof which are incorporated herein by reference in their entirety.

FIELD OF THE DISCLOSURE

The field of the disclosure relates to slurries for polishingsemiconductor substrates and, in particular, polishing slurries thatreduce the roll-off amount for substrates used to produce silicon oninsulator structures.

BACKGROUND

Silicon on insulator structures (“SOI structures” which may also bereferred to herein as “SOI wafers” or “SOI substrates”) generallyinclude a handle wafer, a silicon layer (also characterized as a “devicelayer”), and a dielectric layer (such as an oxide layer) between thehandle wafer and the silicon layer. Transistors built within the topsilicon layer of SOI structures switch signals quickly compared totransistors built on bulk silicon wafers, run at lower voltages and aremuch less vulnerable to signal noise from background cosmic rayparticles. Each transistor is isolated from its “neighbor” or nearbytransistor by a complete layer of silicon dioxide. These transistors aregenerally immune to “latch-up” problems and can be spaced closertogether than transistors built on bulk silicon wafers. Buildingcircuits on SOI structures increases productivity by allowing for morecompact circuit designs, yielding more chips per wafer.

SOI structures may be prepared from silicon wafers sliced from singlecrystal silicon ingots grown in accordance with the Czochralski method.In one method for preparing a SOI structure, a dielectric layer isdeposited on a polished front surface of a donor wafer. Ions areimplanted at a specified depth beneath the front surface of the donorwafer to form a cleave plane, which is generally perpendicular to theaxis, in the donor wafer at the specified depth at which they wereimplanted. The front surface of the donor wafer is then bonded to ahandle wafer and the two wafers are pressed to form a bonded wafer. Aportion of the donor wafer is then cleaved along the cleave plane toremove a portion of the donor wafer leaving behind a thin silicon layer(i.e., the device layer) to form the SOI structure.

A lack of bonding or weak bonding between the dielectric layer and thehandle wafer at the periphery of the bonded structure causes thedielectric layer and/or the silicon layer at the periphery to be removedduring subsequent cleaving. This results in a SOI structure that has asilicon layer (and typically also a dielectric layer) with a smallerradius than the handle wafer. The peripheral region of the structurethat does not include the silicon layer is not available for devicefabrication and is also a potential source of particle contamination.This unusable peripheral region may have a width of at least 1 mm oreven 1.5 mm or more in 200 mm wafers and may include at least about 2.5%of the SOI structure's surface area.

There is a need for methods for manufacturing SOI wafers that allow thesilicon layer of the structure to extend further to the edge of thehandle wafer.

This section is intended to introduce the reader to various aspects ofart that may be related to various aspects of the disclosure, which aredescribed and/or claimed below. This discussion is believed to behelpful in providing the reader with background information tofacilitate a better understanding of the various aspects of the presentdisclosure. Accordingly, it should be understood that these statementsare to be read in this light, and not as admissions of prior art.

SUMMARY

One aspect of the disclosure is directed to a method for polishing asemiconductor substrate. The substrate has a front surface and a backsurface generally parallel to the front surface. The front surface ofthe substrate is contacted with a polishing pad in the presence of apolishing slurry. The polishing slurry includes a first set of silicaparticles that have a silica content of X₁ wt %. The slurry alsoincludes a second set of silica particles that are polymer-encapsulatedand have a silica content of X₂ wt %. X₂ is greater than X₁.

Another aspect of the disclosure is directed to a polishing slurry forpolishing a semiconductor wafer. The polishing slurry includes a firstset of silica particles having a silica content of X₁ wt %. The slurryalso includes a second set of silica particles. The second set of silicaparticles are polymer-encapsulated and have a silica content of X₂ wt %.X₂ is greater than X₁.

Various refinements exist of the features noted in relation to theabove-mentioned aspects of the present disclosure. Further features mayalso be incorporated in the above-mentioned aspects of the presentdisclosure as well. These refinements and additional features may existindividually or in any combination. For instance, various featuresdiscussed below in relation to any of the illustrated embodiments of thepresent disclosure may be incorporated into any of the above-describedaspects of the present disclosure, alone or in any combination.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-section view of a donor structure with a dielectriclayer thereon;

FIG. 2 is cross-section view of the donor structure during ionimplantation;

FIG. 3 is a cross-section view of the donor structure bonded to a handlestructure;

FIG. 4 is a cross-section view of a layered semiconductor structure uponcleaving the donor structure at the cleave plane;

FIG. 5 is a cross-section view of a wafer schematically showingmeasurement of the roll-off amount;

FIG. 6 is a probability plot of the roll-off amount of wafers polishedaccording to Example 1;

FIG. 7 is a graph showing the unbonded width of silicon on insulatorstructures produced according to Example 2;

FIG. 8 is a graph showing the change in flatness between wafers producedwith the polishing slurries of Example 3; and

FIG. 9 is a graph showing the change in roll-off amount between wafersproduced with the polishing slurries of Example 3.

Corresponding reference characters indicate corresponding partsthroughout the drawings.

DETAILED DESCRIPTION

Multi-layered structures and, in particular, silicon on insulatorstructures and methods for producing silicon on insulator structures aregenerally known by those skilled in the art (see, for example, U.S. Pat.Nos. 5,189,500; 5,436,175 and 6,790,747, each of which is incorporatedherein by reference for all relevant and consistent purposes). In anexemplary process for making a multi-layered structure, two separatestructures are prepared, bonded together along a bond interface, andthen delaminated (i.e., cleaved) along a separation plane that isdifferent from the bond interface and which has been formed via animplantation technique. One structure is typically referred to as the“handle” wafer (or structure) and the other is typically referred to asthe “donor” wafer (or structure).

The donor and/or handle wafers used to produce the SOI structure may becomposed of single crystal silicon and may be obtained by slicing thewafers from ingots formed by the Czochralski process. The donor andhandle wafer (and resulting SOI structure) each include a central axis,a front surface and a back surface parallel to the front surface, thefront and back surfaces being generally perpendicular to the centralaxis, a circumferential edge joining the front and back surfaces and aradius extending from the central axis to the circumferential edge. Thehandle wafer and/or the donor wafer used in accordance with the presentdisclosure may be any diameter suitable for use by those of skill in theart including, for example, 200 mm, 300 mm, greater than 300 mm or even450 mm diameter wafers. In some embodiments, the donor wafer and thehandle wafer are 200 mm in diameter.

In one or more embodiments for preparing the donor wafer and/or handlewafer, a polishing step is performed in which the front surface ispolished to achieve a desired surface roughness. The polishing step maybe a single-side polish (i.e., the back surface is not polished) whichis typical for processing of 200 mm substrates. The single-side polishmay reduce the surface roughness of the wafer to less than about 2.0 Åas measured by atomic force microscopy (AFM) at scan sizes of about 10μm×about 10 μm to about 100 μm×about 100 μm. The single-side polish mayeven reduce the surface roughness to less than about 1.5 Å or less thanabout 1.2 Å at scan sizes of about 10 μm×about 10 μm to about 100μm×about 100 μm.

The single-side polish may result in removal of at least about 1 μm ofmaterial from the front surface of the substrate and typically at leastabout 5 μm or even 10 μm or more (e.g., from about 1 μm to about 20 μmand, more typically, from about 5 μm to about 20 μm or 10 to about 20 μmof material from the surface of the wafer). Removal of 1 μm of materialor more from the front surface of the substrate is typical of 200 mmsubstrate processing in which a single polishing step is performed. 300mm substrate processing may involve two polishing steps (a “rough”double side polish with about 10 to about 20 μm of material beingremoved and a “finish” or “mirror” single side polish with less than 1μm of material being removed).

The single-side polish may be achieved by, for example,chemical-mechanical planarization (CMP). CMP typically involves theimmersion of the wafer in an abrasive slurry and polishing of the waferby a polymeric pad. Through a combination of chemical and mechanicalmeans the surface of the wafer is smoothed. Typically the polish isperformed until a chemical and thermal steady state is achieved anduntil the wafers have achieved their targeted shape and flatness.

Suitable polishers for the single-side polish may be obtained fromLapmaster SFT (e.g., LGP-708, Chiyoda-Ku, Japan). In accordance withembodiments of the present disclosure, the pad used for single-sidepolishing is a suede-type pad (also referred to as a polyurethane foampad) such as a SURFIN pad from Fujimi (Kiyoso, Japan), a CIEGAL pad fromChiyoda KK (Osaka, Japan) or a SPM pad from Rohm and Haas. Polyurethaneimpregnated polyethylene pads such as SUBA pads available from Rohm andHaas may also be used.

The single-side polish may occur for at least about 60 seconds or evenabout 90, 120 or 180 seconds or more. The slurry flow rate may rangefrom about 500 ml/min to about 750 ml/min and the pad pressure may rangefrom about 75 g/cm² to about 125 g/cm²; however, it should be understoodthat other polish times, pad pressures and slurry flow rates may be usedwithout departing from the scope of the present disclosure.

In some embodiments of the present disclosure, the single-side polishingslurry is a polydisperse slurry that includes a first set of colloidalsilicon particles and a second set of colloidal silica particles. Thefirst and second sets of silica particles may be amorphous silica andare generally spherical. The first set of silica particles has a silicacontent of X₁ and the second set has a silica content of X₂ with X₂being greater than X₁. The silica content of the particles may be variedby individually encapsulating the particles of at least one set with apolymer with the degree of encapsulation (i.e., thickness of polymer)being different between the two sets. The polymer reduces the silicacontent within the set of particles. In some embodiments, the ratio ofX₂ to about X₁ is at least about 2:1 or even at least about 3:1, atleast about 5:1, at least about 10:1 or even at least about 15:1. Thedifference between X₂ and about X₁ (i.e., X₂ minus X₁) may be about 5 wt%, at least about 10 wt %, at least about 25 wt % or at least about 50wt %.

In some embodiments, the silica particles of the first set areindividually encapsulated in a polymer and the first set includes lessthan about 25 wt % silica or, as in other embodiments, less than about15 wt %, less than about 10 wt %, from about 1 wt % to about 25 wt %,from about 1 wt % to about 15 wt % or from about 1 wt % to about 10 wt %silica.

The second set of silica particles may also be individually polymerencapsulated. The second set of polymer-encapsulated silica particlesmay comprise at least about 50 wt % silica or at least about 60 wt %, atleast about 70 wt %, from about 50 wt % to about 95 wt %, from about 60wt % to about 95 wt % or from about 70 wt % to about 90 wt % silica.

The first set of silica particles and the second set of silica particlesmay be used in a weight ratio (including silica and polymer) from about5:1 to about 1:5 or from about 3:1 to about 1:3, from about 2:1 to about1:2 or from about 4:3 to about 3:4.

The polymers used for encapsulation may be any of the polymersconventionally used in the field of substrate polishing and, inparticular, silicon wafer polishing. The polymer may be a water-solublepolymer such as cellulose, substituted-cellulose, modified starches orxanthan gum.

Both the first and second sets of silica particles have an averageparticle size. Generally the particle sizes are relatively similar tomaintain polishing action of both sets. The difference in the averagediameters between the first and second sets of silica particles may beless than less than about 30 nm, less than about 20 nm or less thanabout 10 nm. The average diameters of the particles of both sets may beless than about 100 nm, less than about 50 nm, from about 10 nm to about50 nm, from about 20 nm to about 40 nm or from about 30 nm to about 40nm. In some embodiments, the average diameter of the first set ofparticles is about 35 nm and/or the average diameter of the second setof particles is about 30 nm.

The polishing slurry is generally a polydisperse colloid in which thetwo sets of solid-phase silica particles are dispersed in a liquidphase. Suitable liquid phases include aqueous solutions. The slurry mayinclude additional components typical of polishing slurries used topolish single crystal silicon wafers. The slurry may be prepared bymixing a first solution containing the first set of silica particleswith a second solution containing the second set of silica particles.For example, the solution may be prepared by separately introducing thetwo solutions to the polishing tool and mixing the solutions at thepolishing pad. In other embodiments, the polishing slurry is preparedoutside of the polisher.

At least one of the handle wafer and the donor wafer are single-sidepolished with the polydisperse polishing slurry (i.e., the slurrycontaining both the first set and second set of silica particles) beforeassembly of the silicon-on-insulator structure. In some embodiments,both the handle wafer and donor wafer are polished with the polydispersepolishing slurry.

In some embodiments, the single side polish process includes contactingthe front surface of the wafer with different polishing slurries atvarious intervals (e.g., to remove the bulk of material in a first step,remove material with roll-off improvement in a second step and to cleanand remove minor scratches in a third step). In some instances, thesubstrate is (1) contacted with a first polishing slurry containingsilica particles of the second set (and not of the first set); (2)contacted with a second polishing slurry containing the first set ofsilica particles and the second set of silica particles; and (3)contacted with a third polishing slurry containing silica particles ofthe first set (and not of the second set). Each sequential polishingstep may be from about 10 seconds to about 3 minutes in length.

After the single-side polish is complete, the wafers may be rinsed anddried. In addition, the wafers may be subjected to a wet bench or spincleaning. Wet bench cleaning may include contacting the wafers with SC-1cleaning solution (i.e., ammonium hydroxide and hydrogen peroxide),optionally, at elevated temperatures (e.g., about 50° C. to about 80°C.). Spin cleaning includes contact with a HF solution and ozonatedwater and may be performed at room temperature.

The silicon on insulator structure may be prepared from the single-sidepolished donor and handle wafers by any of the conventional methods forpreparing such structures. A dielectric layer may be deposited on thesurface of the donor wafer, the handle wafer or both, prior to bondingthe donor and handle together. In this regard, the SOI structures andmethods for preparing the SOI structures are described herein as havinga dielectric layer deposited or grown on the donor wafer and as havingthe surface of the handle wafer bonded to the surface of the dielectriclayer. However, it should be understood that the dielectric layer may begrown or deposited on the handle wafer alternatively or in addition togrowing or depositing the dielectric layer on the donor wafer and thatthese structures may be bonded in any of the various arrangementswithout limitation. Reference herein to the dielectric layer beingdisposed on the handle wafer alone should not be considered in alimiting sense.

Typically, at least the donor wafer and more typically both the donorwafer and the handle wafer are composed of single crystal siliconwafers, however it should be noted that other starting structures may beused such as multi-layered and/or heterolayered structures withoutdeparting from the present disclosure. Generally, the polishing methodsdescribed above are suitable for SOI substrate preparation. Thepolishing methods may also be used for other purposes (e.g., bulk waferproduction). In some embodiments, the substrate that is polished is apolysilicon substrate.

Referring to FIG. 1, a dielectric layer 15 (e.g., a silicon oxide and/orsilicon nitride layer) is deposited on a polished front surface of adonor wafer 12. The dielectric layer 15 may be applied according to anyknown technique in the art, such as thermal oxidation, wet oxidation,thermal nitridation or a combination of these techniques. Generallyspeaking, the dielectric layer 15 is grown to a substantially uniformthickness sufficient to provide the desired insulating properties in thefinal structure. Typically, however, the dielectric layer has athickness of at least about 1 nm and less than about 500 nm, less thanabout 300 nm, less than about 200 nm, less than about 150 nm, less thanabout 100 nm or even less than about 50 nm. The dielectric layer 15 maybe any electrically insulating material suitable for use in a SOIstructure, such as a material comprising SiO₂, Si₃N₄, aluminum oxide, ormagnesium oxide. In one embodiment, the dielectric layer 15 is SiO₂(i.e., the dielectric layer consists essentially of SiO₂). However, itis to be noted that in some instances, it may alternatively bepreferable to use a material for the dielectric layer which has amelting point which is higher than the melting point of pure SiO₂ (i.e.,higher than about 1700° C.). Examples of such materials are siliconnitride (Si₃N₄), aluminum oxide, and magnesium oxide.

In this regard it should be understood that, while the SOI structuresare described herein as having a dielectric layer, in some embodimentsthe dielectric layer is eliminated and the handle wafer and donor waferare “direct bonded.” Reference herein to such dielectric layers shouldnot be considered in a limiting sense. Any one of a number of techniquesknown to those of skill in the art may be used to produce such directbonded structures.

Ions (e.g., hydrogen atoms, helium atoms or a combination of hydrogenand helium atoms) are implanted at a substantially uniform specifieddepth beneath the front surface of the donor wafer to define a cleaveplane 17 (FIG. 2). It should be noted, that when combinations of ionsare implanted, they may be implanted concurrently or sequentially. Ionimplantation may be achieved using means known in the art. For example,this implantation may be achieved in a manner similar to the processdisclosed in U.S. Pat. No. 6,790,747. Implantation parameters mayinclude, for example, implantation of ions to a total dose of about1×10¹⁵ to about 5×10¹⁶ ions/cm² at a total energy of, for example, about20 to about 125 keV (e.g., H₂ ⁺ may be implanted at an energy of 20 keVand a dose of 2.4×10¹⁶ ions/cm²). When a combination of ions is used,the dose may be adjusted between the combination of ions accordingly(e.g., He⁺ may be implanted at an energy of 36 keV and a dose of 1×10¹⁶ions/cm² followed by H₂ ⁺ implanted at an energy of 48 keV and a dose of5×10¹⁵ ions/cm²).

When implantation is performed prior to deposition of the dielectriclayer, the subsequent growth or deposition of the dielectric layer onthe donor wafer is suitably performed at a temperature low enough toprevent premature separation or cleaving along plane 17 in the donorlayer (i.e., prior to the wafer bonding process step). The separation orcleaving temperature is a complex function of the implanted species,implanted dose, and implanted material. However, typically, prematureseparation or cleaving may be avoided by maintaining a deposition orgrowth temperature below about 500° C.

Referring now to FIG. 3, the front surface of the dielectric layer 15 isthen bonded to the front surface of a handle wafer 10 to form a bondedwafer 20 through a hydrophilic bonding process. The dielectric layer 15and handle wafer 10 may be bonded together by exposing the surfaces ofthe wafers to a plasma containing, for example, oxygen or nitrogen.Exposure to the plasma modifies the structure of the surfaces in aprocess often referred to as surface activation. The wafers are thenpressed together and a bond at the bond interface 18 is formedtherebetween.

Prior to bonding, the surfaces of the dielectric layer and handle wafermay optionally undergo cleaning and/or a brief etching, planarization,or plasma activation to prepare their surfaces for bonding usingtechniques known in the art. Without being held to a particular theory,it is generally believed that the quality of the silicon surface of theSOI structure is, in part, a function of the quality of the surfaceprior to bonding. Additionally, the quality of both surfaces prior tobonding will have a direct impact on the quality or strength of theresulting bond interface.

In some instances, therefore, the dielectric layer and/or handle wafermay be subjected to polishing (as described above) and/or cleaning by,for example, a wet chemical cleaning procedure, such as a hydrophilicsurface preparation process (e.g., an RCA SC-1 clean process wherein thesurfaces are contacted with a solution containing ammonium hydroxide,hydrogen peroxide, and water at a ratio of, for example, 1:2:50 at about65° C. for about 20 minutes, followed by a deionized water rinse anddrying). One or both of the surfaces may also optionally be subjected toa plasma activation after, or instead of, the wet cleaning process toincrease the resulting bond strength. The plasma environment mayinclude, for example, oxygen, ammonia, argon, nitrogen, diborane, orphosphine.

Generally speaking, wafer bonding may be achieved using essentially anytechnique known in the art, provided the energy employed to achieveformation of the bond interface is sufficient to ensure that theintegrity of the bond interface is sustained during subsequentprocessing (i.e., layer transfer by separation along the cleave orseparation plane 17 in the donor wafer). Typically, however, waferbonding is achieved by contacting the surface of the dielectric layerand the handle wafer at a reduced pressure (e.g., about 50 mTorr) and atroom temperature, followed by heating at an elevated temperature (e.g.,at least about 200° C., at least about 300° C., at least about 400° C.,or even at least about 500° C.) for a sufficient period of time (e.g.,at least about 10 seconds, at least about 1 minute, at least about 15minutes, at least about 1 hour or even at least about 3 hours). Forexample, the heating may take place at about 350° C. for about 1 hour.The resulting interface may have a bond strength that is greater thanabout 500 mJ/m², greater than about 1000 mJ/m², greater than about 1500mJ/m², or even greater than about 2000 mJ/m². The elevated temperaturescause the formation of covalent bonds between the adjoining surfaces ofthe donor wafer and the handle wafer, thus solidifying the bond betweenthe donor wafer and the handle wafer. Concurrently with the heating orannealing of the bonded wafer, the ions earlier implanted in the donorwafer weaken the cleave plane. A portion of the donor wafer is thenseparated (i.e., cleaved) along the cleave plane from the bonded waferto form the SOI structure.

After the bond interface has been formed, the resulting bonded structureis subjected to conditions sufficient to induce a fracture along theseparation or cleave plane within the donor wafer (FIG. 4). Generallyspeaking, this fracture may be achieved using techniques known in theart, such as thermally and/or mechanically induced cleaving techniques.Typically, however, fracturing is achieved by annealing the bondedstructure at a temperature of at least about 200° C., at least about300° C., at least about 400° C., at least about 500° C., at least about600° C., at least about 700° C. or even at least about 800° C. (thetemperature being in the range of, for example, about 200° C. to about800° C., or from about 250° C. to about 650° C.) for a period of atleast about 10 seconds, at least about 1 minute, at least about 15minutes, at least about 1 hour or even at least about 3 hours (withhigher temperatures requiring shorter anneal times, and vice versa),under an inert (e.g., argon or nitrogen) atmosphere or ambientconditions.

In this regard it is to be noted that in an alternative embodiment, thisseparation may be induced or achieved by means of mechanical force,either alone or in addition to annealing. For instance, the bonded wafermay be placed in a fixture in which mechanical force is appliedperpendicular to the opposing sides of the bonded wafer in order to pulla portion of the donor wafer apart from the bonded wafer. According tosome methods, suction cups are utilized to apply the mechanical force.The separation of the portion of the donor wafer is initiated byapplying a mechanical wedge at the edge of the bonded wafer at thecleave plane in order to initiate propagation of a crack along thecleave plane. The mechanical force applied by the suction cups thenpulls the portion of the donor wafer from the bonded wafer, thus forminga SOI structure.

Referring to FIG. 4, upon separation, two structures 30, 31 are formed.Since the separation of the bonded structure 20 occurs along the cleaveplane 17 in the donor wafer 12 (FIG. 2), a portion of the donor waferremains part of both structures (i.e., a portion of the donor wafer istransferred along with the dielectric layer). Structure 30 comprises aportion of the donor wafer. Structure 31 is the silicon on insulatorstructure and includes the handle wafer 16, the dielectric layer 15, anda silicon layer 25.

The resulting SOI structure 31 includes a thin layer of silicon 25 (theportion of the donor wafer remaining after cleaving) disposed atop thedielectric layer 15 and the handle wafer 10. The cleave surface of theSOI structure (i.e., the thin layer of silicon of the donor wafer) has arough surface that may be smoothed by additional processing. Thestructure 31 may be subjected to additional processing to produce asilicon layer surface having desirable features for device fabricationthereon. Such features include, for example, reduced surface roughness,and/or a reduced concentration of light point defects.

In accordance with the present disclosure, the donor wafer and/or thehandle wafer used to prepare the SOI structure have a roll-off amount(ROA) less than many conventional donor and/or handle wafers (andparticularly 200 mm wafers) to improve the bonding between thedielectric layer and the handle wafer at the peripheral edge portions ofthe bonded structure. ROA may generally be determined by well-knownindustry measurement protocols. Particularly, ROA may be measured usingthe height data profile as disclosed by M. Kimura et al., “A New Methodfor the Precise Measurement of Wafer Roll off of Silicon PolishedWafer,” Jpn. Jo. Appl. Phys., vol. 38, pp. 38-39 (1999), which isincorporated herein by reference for all relevant and consistentpurposes. Generally, the methods of Kimura have been standardized by theindustry as by, for example, SEMI M69: Practice for Determining WaferNear-Edge Geometry using Roll-off Amount, ROA (Preliminary) (2007) whichis also incorporated herein by reference for all relevant and consistentpurposes. Most commercially available wafer-inspection instruments arepre-programmed to calculate ROA. For instance ROA may be determined byuse of a KLA-Tencor Wafer Inspection System using WaferSight analysishardware (Milpitas, Calif.).

With reference to FIG. 5, ROA of a wafer 20 is generally determined byreference to three points (P₁, P₂ and P₃) along a wafer radius. Areference line R is fitted between two points (P₁, P₂) and the thirdpoint (P₃) near the circumferential edge of the wafer where roll-off isconventionally observed. The ROA is the distance between the referenceline R and the third point P₃. The reference line R may be fitted as afirst order linear line or a third order polynomial. For purposes of thepresent disclosure, the reference line is fitted as a first order linearline unless stated differently.

In this regard, ROA may be expressed in terms of front surface ROA, backsurface ROA or thickness ROA (i.e., using an average thickness profile).Front surface ROA and back surface ROA measurements involve fitting abest-fit reference line R between P₁ and P₂ along the respective frontor back surface and thickness ROA involves fitting a best fit line forthe various wafer 20 thicknesses between P₁ and P₂ (i.e., the thicknessROA takes into account both the front and back surface). In this regard,it has been found that the thickness ROA better correlates to improvedbonding in the bonded structure and to the distance to which the siliconlayer extends to the wafer edge in the resulting SOI structure ascompared to the front surface ROA. Roll-off amounts recited herein arethickness ROA measurements unless stated otherwise.

While any of three points may be chosen to determine ROA, one commonmethod used in the art, particularly for 200 mm substrates, includesusing a first point that is about 90% of the radius of the wafer fromthe central axis of the wafer and a second point that is about 94% ofthe radius from the central axis of the wafer to form the reference lineR. These points are about 90 mm and 94 mm from the central axis of thewafer in a 200 mm diameter wafer. A third point about 96% of the radiusof the wafer from the central axis (i.e., at about 96 mm from thecentral axis for a 200 mm diameter wafer) may be used with the distancebetween the reference line and the third point being ROA.

ROA may be measured across several radii of the wafer and averaged. Forinstance, the ROA of 2, 4 or 8 radii angularly spaced across the wafermay be measured and averaged. For instance, ROA may be measured byaveraging the ROA of eight radii (e.g., the eight radii at 0°, 45°, 90°,135°, 180°, 225°, 275° and 315° in the R-θ coordinate system asdescribed in SEMI M69).

It should be understood that ROA, in regard to the thickness profile,may be a positive number in which the wafer becomes thicker nearer itscircumferential edge or may be a negative number in which the waferbecomes less thick towards the circumferential edge. In this regard, useof the phrase “less than” herein in relation to an ROA amount (eithernegative or positive) indicates that the ROA is in a range from therecited amount to about 0 (e.g., an ROA of “less than about −70 nm”refers to an ROA range of about −70 nm to about 0 and an ROA of “lessthan about 70 nm” refers to an ROA in the range of about 70 nm to about0). Additionally, use of the phrase “greater than” in relation to an ROAamount (either negative or positive) includes roll-off amounts in whichthe edge portion of the wafer is further away from the axial center ofthe wafer than the recited amount.

In accordance with embodiments of the present disclosure, 200 mm donorwafers and/or handle wafers processed with the polydisperse polishingslurry may have a ROA (measured with reference line formed at 90 mm and94 mm compared to the thickness at 96 mm) of less than about −40 nm. Inother embodiments, the ROA of the donor wafer is less than about −35 nm,less than about −20 nm, less than about 0 nm or from about −35 nm toabout 25 nm.

With reference to FIG. 6, use of the polydisperse polishing slurrydecreases the average ROA in a population of wafers. In embodiments inwhich a population of wafers (e.g., at least 5, 10, 25 or 100 or morewafers) is polished with the polishing slurry, at least about 20% of thewafers may have a roll-off amount of less than about −35 nm or even atleast about 40%, at least about 60% or at least about 60% of the wafershave a roll-off amount of less than about −35 nm.

By reducing the ROA of the handle and/or donor wafers, bonding betweenthe dielectric layer and the handle wafer at the peripheral edgeportions of the bonded structure is improved (i.e., voids are reduced,bonded area is increased, and bonding extends closer to thecircumferential edge) as compared to bonded structures that are producedfrom conventional handle and donor wafers. As a result of the improvedbonding, the silicon layer of the resulting SOI structure extends closerto the edge of the handle wafer to which it is bonded after cleaving. In200 mm bonded structures (i.e., before cleaving), the dielectric layermay at least be partially bonded to the handle wafer such that bondsextend from the central axis of the bonded silicon on insulatorstructure to at least 98.2 mm from the central axis of the bondedsilicon on insulator structure and, in some embodiments, to at leastabout 98.5 mm or even at least about 98.6 mm from the central axis ofthe bonded structure (e.g., from about 98.2 mm to about 98.8 mm or fromabout 98.5 mm to about 98.8 mm).

To determine the extent to which bonding occurs in the bonded structure,the bonded wafer may be cleaved in half and analyzed or the resultingSOI structure may be analyzed for the presence of the silicon layer. Inthis regard, the phrase “at least partially bonded” may includearrangements in which bonds extend to the circumferential edge of thehandle and/or donor wafer unless stated otherwise. In this regard itshould be understood that, in certain embodiments, the radius of thehandle wafer may differ from that that of the dielectric layer and/orthe silicon layer (e.g., in the SOI structure after cleaving as a resultof partial bonding) and, as used herein, the “radius of the SOIstructure” refers to the radius of the handle wafer unless statedotherwise.

This increase in peripheral bonding in the bonded structure allows thesilicon layer and the dielectric layer to extend closer to thecircumferential edge of the handle wafer to which they are bonded in theresulting SOI structure. In several exemplary embodiments, the resultingSOI structure includes a silicon layer (and typically also a dielectriclayer) that extends from the central axis of the handle wafer to about98.2 mm from the central axis of the handle wafer and, in someembodiments, to at least about 98.5 mm or even at least about 98.6 mmfrom the central axis of the handle wafer structure (e.g., from about98.2 mm to about 98.8 mm or from about 98.5 mm to about 98.8 mm).

The extent to which the silicon layer extends to the edge of the handlewafer may be determined by, for example, viewing the structure under anoptical microscope (e.g., with a 5× objective) such as a Nomarskidifferential interference contrast (DIC) microscope.

In this regard, it should be understood that, as used herein, the widthof the unbonded portion does not include the beveled region of thewafer. Stated differently, the unbonded region extends from the edge ofthe beveled region to the edge of the silicon layer rather than from theapex to the silicon layer edge.

The SOI structure formed after cleaving the donor wafer at the cleaveplane may be characterized with ROA's at the various wafer interfacesthat are substantially similar to the ROA of the handle wafer and/ordonor wafer which are used to produce the SOI structure. In 200 mmwafers, the handle wafer may have an ROA (measured with reference lineformed at 90 mm and 94 mm compared to the thickness at 96 mm) of lessthan about −40 nm at the interface with the dielectric layer. In otherembodiments, the ROA of the handle wafer is less than about −35 nm, lessthan about −20 nm, less than about 0 nm or from about −35 nm to about 25nm at the interface with the dielectric layer.

As compared to conventional methods for polishing substrates, methods ofthe present disclosure have several advantages. Use of a polishingslurry having two sets of colloidal silica particles with one set havinga greater weight percentage of silica within the particles (and lesspolymer) may reduce the ROA of the wafer (e.g., at 96 mm from thecentral axis in 200 mm substrates). Silica particles having a thickerpolymer coating have less polishing action at low pad pressures comparedto silica particles having less or no polymer. Particles with lesspolymer act to polish more uniformly regardless of pad pressure. Byincluding two sets of silica particles with different amounts ofpolymer, the polishing rate across the wafer may vary depending onwhether roll-off is observed with at least some base-level polishingoccurring across the wafer. At the center of the wafer where roll-offdoes not occur, the pad pressure allows both sets of particles to act topolish the wafer and remove material. At the edge of the wafer whereroll-off is observed, the pad pressure is reduced which reduces the rateof polishing, particularly the rate attributed to the particles havingmore polymer.

Use of a polishing slurry having two sets of colloidal silica particleswith one set having a greater amount of silica (and less polymer) maypush the roll-off closer to the edge of the wafer, possibly even beyonda flatness inspection area. In this manner, the flatness relatively nearthe wafer edge is improved.

The polishing slurry may be particularly useful to reduce the ROA insingle-side polishing processes in which at least about 5 μm or even atleast 10 μm of material from the surface of the wafer is removed (whichis typical of polishing of 200 mm diameter wafers). In embodiments inwhich silicon on insulators are produced, use of a polishing slurryhaving one set of silica particles with more polymer than the other setimproves bonding in the bonded structure, particularly in embodiments inwhich both the donor and handle wafer are polished by the slurry.

EXAMPLES

The processes of the present disclosure are further illustrated by thefollowing Examples. These Examples should not be viewed in a limitingsense.

Example 1: Effect of Polishing Slurry on ROA

A first set of single crystal silicon wafers (200 mm) were single-sidepolished with a polishing slurry containing polymer-encapsulatedcolloidal silica for about 240 seconds. The polishing slurry containedcolloidal silica (23.6 wt %; Nalco DVSTS029) diluted with 76.4 wt %deionized water. The polishing slurry also included a small amount of 31wt % H₂O₂ (about 2.7×10⁻⁴ wt %). The polymer-encapsulated silicaparticles included about 80 wt % silica (with the remainder beingpolymer) and had an average particle diameter of about 30 nm. The firstset was then single side polished for 30 seconds with a colloidal silicaslurry having an average particle size of about 35 nm (Glanzox-3103).

A second set of silicon wafers (200 mm) were also single-side polishedwith the polishing slurry containing polymer-encapsulated colloidalsilica particles with 80% silica (colloidal silica—23.6 wt % (NalcoDVSTS029); DI water—76.4 wt %; 31 wt % H₂O₂—2.7×10⁻⁴ wt %) for about 140seconds.

The second set of wafers were then single-side polished for about 127seconds with a polishing slurry containing a first set of silicaparticles containing 80% silica (Nalco DVSTS029) and a second set ofsilica particles containing about 5% silica (with the remainder beingpolymer) with an average particle size of about 35 nm (Glanzox-3103).The polishing slurry was prepared by piping the slurry of the firstpolishing step and the commercial 35 nm suspension to the polishing padwhere the slurries combined at the pad. The weight ratio between thesilica particles of the first set and the second set (including silicaand polymer) was about 1:1.

The second set of wafers were then single-side polished for 30 secondswith a colloidal silica slurry having silica particles containing about5 wt % silica and an average particles size of about 35 nm(Glanzox-3103).

A probability plot showing the ROA distribution for the two sets ofwafers is shown in FIG. 6. The ROA was measured by forming a first orderreference line at 90 mm and 94 mm and measuring the distance to thereference line at 96 mm. As shown in FIG. 6, the new polishing slurryimproved ROA measured 96 mm by more than 25 nm (i.e., pushed theroll-off closer to the wafer circumferential edge).

Example 2: Effect of Polishing Slurry on ROA

The first set of wafers of Example 1 were used as donor and handlewafers to produce silicon on insulator structures (200 mm) having a SiO₂dielectric layer. The second set of wafers were also used as donor andhandle wafers to produce silicon on insulator structures (200 mm) havinga SiO₂ dielectric layer. The unbonded region of the silicon on insulatorstructures made from the first set of wafers (“Conventional Slurry”) andthe second set of wafers (New Slurry”) is shown in FIG. 7. The SOIstructures made from donor and handle wafers polished by the new slurryhad an unbonded region from about 1.2 mm to about 1.8 mm (about 98.8% toabout 98.2% of the radius) while the silicon on insulator structuresproduced from donor and handle wafers polished by the conventionalslurry recipe had a larger unbonded region of about 1.5 mm to about 2.2mm (about 98.5% to about 97.8% of the radius).

Example 3: Effect of Polishing Time on Flatness and ROA

Single crystal silicon wafers (200 mm) were single side polished with apolishing slurry containing colloidal silica particles with 80 wt %silica (colloidal silica—23.6 wt % (Nalco DVSTS029); DI water—76.4 wt %;31 wt % H₂O₂— 2.7×10⁻⁴ wt %) with an average particle diameter of about30 nm for about 140 seconds. The wafers were then single-side polishedwith a polishing slurry containing a first set of silica particlescontaining about 80 wt % silica and an average particle diameter ofabout 30 nm (Nalco DVSTS029) and a second set of silica particlescontaining about 5 wt % silica with an average particle size of about 35nm (Glanzox-3103). The polishing slurry was prepared by mixing theslurry of the first polish step with the commercial 35 nm suspension atthe polishing pad. The weight ratio between the first set of silicaparticles and the second set (including silica and particles) was about1:1. The polishing time with the second slurry was varied as shown inFIGS. 8 and 9. The second set of wafers was then single-side polishedfor 30 seconds with a colloidal silica slurry having silica particleswith about 5 wt % silica (Glanzox-3103).

The flatness (SFQR) of the wafers was determined and compared to theaverage flatness of wafers polished by the conventional recipe ofExample 1. The change in flatness is shown in FIG. 8. Wafer flatnessimproved initially with additional polishing time and worsened at about210 seconds.

The roll-off amount of the wafers was also determined and compared tothe average ROA of wafers polished by the conventional recipe ofExample 1. The change in ROA is shown in FIG. 9. FIG. 9 shows a positivenumber ROA change for most samples which indicates the ROA of waferspolished by the new slurry improved (i.e., was a smaller negativenumber). As shown in FIG. 9, the ROA improved with longer polishingtimes.

As used herein, the terms “about,” “substantially,” “essentially” and“approximately” when used in conjunction with ranges of dimensions,concentrations, temperatures or other physical or chemical properties orcharacteristics is meant to cover variations that may exist in the upperand/or lower limits of the ranges of the properties or characteristics,including, for example, variations resulting from rounding, measurementmethodology or other statistical variation.

When introducing elements of the present disclosure or the embodiment(s)thereof, the articles “a”, “an”, “the” and “said” are intended to meanthat there are one or more of the elements. The terms “comprising,”“including,” “containing” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements. The use of terms indicating a particular orientation (e.g.,“top”, “bottom”, “side”, etc.) is for convenience of description anddoes not require any particular orientation of the item described.

As various changes could be made in the above constructions and methodswithout departing from the scope of the disclosure, it is intended thatall matter contained in the above description and shown in theaccompanying drawing[s] shall be interpreted as illustrative and not ina limiting sense.

What is claimed is:
 1. A polishing slurry for polishing a semiconductorwafer, the polishing slurry comprising: a first set of silica particles,the silica particles having a silica content of X₁ wt %; a second set ofsilica particles, the second set of silica particles beingpolymer-encapsulated and having a silica content of X₂ wt %, wherein X₂is greater than X₁.
 2. The polishing slurry as set forth in claim 1wherein the first set of silica particles are polymer-encapsulated. 3.The polishing slurry as set forth in claim 2 wherein the polymer isselected from the groups consisting of cellulose, substituted-cellulose,modified starches and xanthan gum.
 4. The polishing slurry as set forthin claim 1 wherein the ratio of X₂ to about X₁ is at least about 2:1. 5.The polishing slurry as set forth in claim 1 wherein the ratio of X₂ toabout X₁ is at least about 3:1.
 6. The polishing slurry as set forth inclaim 1 wherein the ratio of X₂ to about X₁ is at least about 5:1. 7.The polishing slurry as set forth in claim 1 wherein the ratio of X₂ toabout X₁ is at least about 10:1.
 8. The polishing slurry as set forth inclaim 1 wherein the ratio of X₂ to about X₁ is at least about 15:1. 9.The polishing slurry as set forth in claim 1 wherein the first set ofsilica particles contains less than about 15 wt % silica and the secondset contains at least about 50 wt % silica.
 10. The polishing slurry asset forth in claim 1 wherein the first set of silica particles and thesecond subset of silica particles each have an average diameter of lessthan about 100 nm and the difference between the average diameter of thefirst set of particles and the average diameter of the second set ofparticles is less than about 30 nm.
 11. The polishing slurry as setforth in claim 1 wherein the first set of silica particles and thesecond subset of silica particles each have an average diameter of lessthan about 100 nm and the difference between the average diameter of thefirst set of particles and the average diameter of the second set ofparticles is less than about 20 nm.
 12. The polishing slurry as setforth in claim 1 wherein the weight ratio of the first set of silicaparticles to the second set of silica particles is from about 5:1 toabout 1:5.
 13. The polishing slurry as set forth in claim 1 wherein theweight ratio of the first set of silica particles to the second set ofsilica particles is from about 3:1 to about 1:3.
 14. The polishingslurry as set forth in claim 1 wherein the polishing slurry is acolloid.
 15. The polishing slurry as set forth in claim 1 wherein adifference between X₂ and about X₁ is at least about 5%.
 16. Thepolishing slurry as set forth in claim 1 wherein a difference between X₂and about X₁ is at least about 25%.
 17. The polishing slurry as setforth in claim 1 wherein a difference between X₂ and about X₁ is atleast about 50%.
 18. The polishing slurry as set forth in claim 1wherein the first set of silica particles contains less than about 10 wt% silica and the second set contains at least about 70 wt % silica. 19.The polishing slurry as set forth in claim 1 wherein the polishingslurry comprises an aqueous solution.